Abstract

The objective of this thesis is to compare the upper bound of the ground state energy of doubly ionized carbon (C⁺⁺) to the lower bound obtained by reduced density matrices.

To make a fair comparison, the number of orbitals used in both is the same, namely ten. The upper bound is obtained by use of the standard Rayleigh-Ritz Variational Principle which states ⟨Ψ|H|Ψ⟩ ≥ Eo(H) were Eo(H) is the exact ground state energy, H is the Hamiltonian, and Ψ is the trial wave function.

Abstract

A recently developed theory enabling the construction of density matrices which are expressible in terms of a given spin geminal set and which are a nearly N-representable as possible is discussed.

Calculation of lower bounds to the ground state energy of the C⁺⁺ ion is performed utilizing reduced density matrices subject to the continuously variable N-representability constraint determined by the above mentioned theory.

Abstract The objective of this paper is to demonstrate the usefulness of density matrix techniques in the determination of the ground state energy of certain atomic systems. Use of the method, currently under development, results in a lower energy bound in contrast with the Rayleigh-Ritz method which yields an upper bound. The former technique is illustrated for the C⁺⁺ atomic system. It was found that the Pauli Principle was being violated even when the 2-particle density matrix is expanded in...

Abstract The non-relativistic energies have been determined for the singlet and triple S states (1¹S, 2¹S and 2³S) of the helium like two electron system. Calculations were based on a finite set of orbitals of the order 7. The set, which includes Laguerre polynomials, is expressed as a superposition of configurations built up from one-electron wave functions or orbitals and approximates the exact wave function. Application of the variational principle leads to a system of linear equations....